Study on the effect of surface area on the thermal behavior of crude oils with different properties

doi:10.11949/0438-1157.20201599

Abstract

Abstract:

Focusing on the air injection development mechanism of light and heavy oil reservoirs, typical light and heavy oil samples were selected for thermogravimetric experiments, and the thermal behavior and kinetics characteristics of crude oil at three oxidation stages were comparatively analyzed by the conversion method of Ozawa- Fynn-Wall, and the effect of surface effect on the oxidation reaction of light and heavy crude oil was also discussed. The results showed that: ①There is a transition zone between each oxidation stage, and the accurate selection of conversion rate is very important for kinetic parameters. ②The oxidation characteristics of light and heavy crude oil at different oxidation stages are obviously different. Light crude oil is mainly oxidized at low temperature, while fuel deposition and high temperature oxidation are not significant. Moreover, the initial temperature of low temperature oxidation, fuel deposition and high temperature oxidation stage of light oil is lower, which is more likely to induce oxidation reaction. Fuel deposition and high temperature oxidation of heavy oil are significant, and the oxidation reaction rate is faster. ③The surface area effect causes the low temperature oxidation activation energy of light oil to decrease by more than 15%, and the peak temperature decreases by 7—17℃. The deposition and high temperature oxidation of heavy oil fuels are significantly enhanced, and the burn-out temperature drops by 10—17℃.

Key words: light and heavy oil, thermodynamics, kinetics, porous media, air displacement

摘要：

针对轻、重质油油藏注空气开发机理，选取典型轻、重质油样进行热重实验，采用改进的Ozawa-Flynn-Wall等转化率法对比分析了不同性质原油三种氧化阶段的热行为和动力学特征，同时探讨了表面积效应对轻、重质原油氧化反应的影响。研究表明：①各氧化阶段之间存在过渡区域，转化率的准确选取对动力学参数至关重要。②轻、重质原油不同氧化阶段的氧化特征存在明显差异，轻质油以低温氧化为主，燃料沉积和高温氧化不显著，且低温氧化、燃料沉积、高温氧化阶段的起始温度更低，更易诱发氧化反应；重质油燃料沉积和高温氧化显著，氧化反应速度更快。③表面积效应导致轻质油低温氧化活化能降低15%以上，峰值温度降低7~17℃。重质油燃料沉积和高温氧化显著增强，燃尽温度下降10~17℃。

关键词: 轻、重质原油, 热力学, 动力学, 多孔介质, 空气驱

CLC Number:

TE 341

CHEN Hao, LIU Xiliang, TAN Xianhong, TIAN Xiaofeng, YANG Shenglai, YANG Ran, ZHANG Chao. Study on the effect of surface area on the thermal behavior of crude oils with different properties[J]. CIESC Journal, 2021, 72(6): 3338-3348.

陈浩, 刘希良, 谭先红, 田虓丰, 杨胜来, 杨冉, 张超. 表面积效应对不同性质原油热力学行为影响研究[J]. 化工学报, 2021, 72(6): 3338-3348.

Figures/Tables 12

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转化率α	斜率	活化能E/ (kJ·mol^-1)	相关系数R²
0.1	-4122.4	32.58	0.959
0.2	-4678.9	36.98	0.962
0.3	-5145.4	40.66	0.961
0.4	-5575.2	44.06	0.969
0.5	-6192.5	48.94	0.978
0.6	-6911.9	54.63	0.985
0.7	-7853.7	62.07	0.989
0.8	-9493.2	75.03	0.991
0.9	-11672.1	92.24	0.998
1.0	-19857.0	156.93	0.986

转化率α	斜率	活化能E/ (kJ·mol^-1)	相关系数R²
0.1	-4122.4	32.58	0.959
0.2	-4678.9	36.98	0.962
0.3	-5145.4	40.66	0.961
0.4	-5575.2	44.06	0.969
0.5	-6192.5	48.94	0.978
0.6	-6911.9	54.63	0.985
0.7	-7853.7	62.07	0.989
0.8	-9493.2	75.03	0.991
0.9	-11672.1	92.24	0.998
1.0	-19857.0	156.93	0.986

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
轻质油	5	25~387	260	86.9	387~481	458	5.8	481~574	526	7.2	574
	10	25~402	298	85	402~505	475	7.6	505~616	544	7.4	616
	15	25~413	310	85.6	413~517	488	6.8	517~633	562	7.6	633
	20	25~434	331	86.1	434~535	498	7	535~653	580	6.6	653
表面积效应+ 轻质油	5	25~416	253	88.3	416~474	468	4.1	474~562	496	7.6	562
	10	25~429	293	88	429~495	489	5.6	495~605	531	5.9	605
	15	25~440	304	87.1	440~510	482	4.9	510~610	549	8.0	610
	20	25~450	314	87.5	450~516	517	4.3	517~632	563	8.1	632

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
轻质油	5	25~387	260	86.9	387~481	458	5.8	481~574	526	7.2	574
	10	25~402	298	85	402~505	475	7.6	505~616	544	7.4	616
	15	25~413	310	85.6	413~517	488	6.8	517~633	562	7.6	633
	20	25~434	331	86.1	434~535	498	7	535~653	580	6.6	653
表面积效应+ 轻质油	5	25~416	253	88.3	416~474	468	4.1	474~562	496	7.6	562
	10	25~429	293	88	429~495	489	5.6	495~605	531	5.9	605
	15	25~440	304	87.1	440~510	482	4.9	510~610	549	8.0	610
	20	25~450	314	87.5	450~516	517	4.3	517~632	563	8.1	632

原油类型	升温速率/ (℃/min)	LTO			FD			HTO			燃尽温度/℃
原油类型	升温速率/ (℃/min)	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	区间/℃	峰值/℃	质量损失/%	燃尽温度/℃
重质油	5	25~374	328	49.2	374~466	440	21.0	466~549	509	29.1	549
	10	25~393	348	48.9	393~487	453	22.8	487~590	532	27.2	590
	15	25~400	358	48.1	400~502	475	26.8	502~611	551	25.1	611
	20	25~408	369	47.3	408~521	492	28.5	521~633	574	23.9	633
表面积效应+ 重质油	5	25~357	317	48.3	357~479	432	23.9	479~535	495	26.6	535
	10	25~375	331	47.4	375~495	443	25.1	495~573	509	24.3	573
	15	25~402	343	46.6	402~511	471	28.9	511~601	517	23.8	601
	20	25~405	354	46.1	405~514	490	30.3	514~619	538	22.5	619